混合金属钴钌原子簇Co3Ru(CO)11(NO)2, (RC≡CR^1)Co3Ru(CO)9(NO)的合成与表征

本文报道Co-Ru簇的合成与表征的研究。由Et4N[RuCl4(CH3CN)2]和Co2(CO)8制备了Et4N[Co3Ru(CO)12]·1/3THF, 它与等摩尔的NOBF4反应得到Co3Ru(CO)11(NO)(1)和Co2Ru(CO)11(5)。簇合物1分别与乙炔、苯基乙炔和二苯基乙炔进一步反应得到(HC≡CH)Co3Ru(CO)9(NO)(2), (PhC≡CH)Co3Ru(CO)9(NO)(3)和(PhC≡CPh)Co3Ru(CO)9(NO)(4)。在上述反应中还分离得到(HC≡CH)Co2Ru(CO)9(6), (PhC≡CH)Co2Ru(CO)9(7)和(PhC≡CPh)Co2Ru(CO)9(8)。对所得族合物1,2,3,4进行了IR, UV,^1H NMR, m.p., 元素分析和单晶X射线衍射分析等性质表征, 簇合物3的晶体属单斜晶系, pα1/n空间群, 晶胞参数为: a=1.1438(9), b=.3033(6), c=1.4345(9)nm, β=100.72(4)°, 每个晶胞中有四个分子。     

混合金属钴钌原子簇Co3Ru(CO)11(NO)2, (RC≡CR^1)Co3Ru(CO)9(NO)的合成与表征

本文报道Co-Ru簇的合成与表征的研究。由Et4N[RuCl4(CH3CN)2]和Co2(CO)8制备了Et4N[Co3Ru(CO)12]·1/3THF, 它与等摩尔的NOBF4反应得到Co3Ru(CO)11(NO)(1)和Co2Ru(CO)11(5)。簇合物1分别与乙炔、苯基乙炔和二苯基乙炔进一步反应得到(HC≡CH)Co3Ru(CO)9(NO)(2), (PhC≡CH)Co3Ru(CO)9(NO)(3)和(PhC≡CPh)Co3Ru(CO)9(NO)(4)。在上述反应中还分离得到(HC≡CH)Co2Ru(CO)9(6), (PhC≡CH)Co2Ru(CO)9(7)和(PhC≡CPh)Co2Ru(CO)9(8)。对所得族合物1,2,3,4进行了IR, UV,^1H NMR, m.p., 元素分析和单晶X射线衍射分析等性质表征, 簇合物3的晶体属单斜晶系, pα1/n空间群, 晶胞参数为: a=1.1438(9), b=.3033(6), c=1.4345(9)nm, β=100.72(4)°, 每个晶胞中有四个分子。     

(p-CH3OC6H4)2TeO存在下M2(CO)10(M=Mn,Re)的CO取代反应动力学研究

测定了(p-CH₃OC₆H₄)₂TeO存在下M₂(CO)₁₀(M=Mn,Re)的CO取代反应速率及活化参数。其表观速率常数分别与M₂(CO)₁₀和(p-CH₃OC₆H₄)₂TeO的浓度的一次方成正比。本文所建议的缔合机理与前人用(CH₃)₃NO作氧原子转移试剂的相应反应所提出的机理相似。讨论了在(CH₃)₃NO和(p-CH₃OC₆H₄)₂TeO存在下影响M₂(CO)₁₀的CO取代反应速率的因素。     

金属-金属键形成反应的研究: [η^5-RO~2CC~5H~4(CO)~3M]~2Hg(R=Me,Et;M=Cr,Mo,W)的合成及鉴定

η~5-RO_2CC_5H_4(CO)_3MNa(1)与R~1HgCl(2,R~1=Me,Et,Ph)可发生一种非预期的金属键形成反应,生成[η~5-RO_2CC_5H_4(CO)_3M]_2Hg(3a—3f)(R=Me,Et;M=Cr,Mo,W)。对反应中间物η~5EtQ_2CC_5H_4(CO)_3MoHgPh的研究表明:反应是按缩合及对称化两步机理进行的。3e(R=Et,M=Mo)属三斜晶系,空间群P-1。a=0.6333(1),b=0.7712(1),c=1.4204(4)nm;a=77.31(1),β=74.51(2),γ=68.72(1)°;V=0.61714nm~3;Z=1;D_x=2.246g/cm~3;R=0.044.     

M3（CO）12（M=Fe,Ru,Os）的氧原子转移反应动力学

近期研究表明,M(CO)_6(M=Cr,Mo,W)与Me_3NO作用是缔合反应,Me_3NO中氧原子亲核进攻羰基碳,使其以CO_2的形式脱离金属原子,由此产生的活性中间体M(CO)_5与外来配体快速反应生成M(CO)_5L。有关金属原子簇羰基配合物的类似反应动力学研究尚未见报道。原子簇配合物可能表现出与单核配合物不同的反应性质,并且是有效的均相催化剂,进一步了解其与Me_3NO的反应性质颇有意义。本文报道在Me_3NO存在下M_3(CO)_(12)的CO取代反应(1)的研究结果(M=Fe,Ru,Os)。     

金属-金属键形成反应的研究: [η^5-RO~2CC~5H~4(CO)~3M]~2Hg(R=Me,Et;M=Cr,Mo,W)的合成及鉴定

η^5-RO~2CC~5H~4(CO)~3MNa与R^1HgCl,R^1=Me, Et, Ph)可发生一种非预期的金属键形成反应, 生成[η^5-RO~2CC~5H~4(CO)~3M]~2Hg(R=Me,Et;M=Cr,Mo,W)。对反应中间物η^5-EtO~2CC~5H~4(CO)~3MoHgPh的研究表明: 反应是按缩合及对称化两步机理进行的。(R=Et,M=Mo)属三斜晶系, 空间群P-1。a=0.6333(1), b=0.7712(1), c=1.4204(4)nm; a=77.31(1),β=74.51(2), γ=68.72(1)^°; V=0.61714nm^3;Z=1;D~x=2.246g/cm^3;R=0.044。     

Me_3NO存在下Ir_4(CO)_(11)L(L=CO,PPh_3)的CO取代反应动力学研究

刊用FT-IR和UV技术跟踪反应进程,研究了在Me_3NO存在下Ir_4(CO)_(12)和Ir_4(CO)_(11)PPh_3分别在CHCl_3—C_2H_5OH和CHCl_3溶剂中取代羰基反应的动力学与机理。结果表明反应遵循二级速率定律:r=k_2[Me_3NO][配合物]。该速率方程与缔合机理相一致。将Ir_4(CO)_(11)L和Os_3(CO)_(11)L(L=CO,PPh_3)体系的动力学结果相比较,着重讨论了桥基因素对反应活性的影响。     

含膦配体的羰基钼(O)和钨(O)化合物的改进合成,反应及催化活性

MoCl5或WCl6与锌粉及适当的膦配体和CO在常压常温进行反应,合成了含膦配体的炭基钼和钨的化合物(Ph2PR)nM(CO)6-n(M=Mo,W;R=ME,Et,n-Pr,Ph;n=2,3),用该方法也成功地将M(CO)5(M=Mo,W)单元负载到含膦的高分子链上,化合物(Ph2PEt)2Mo(CO)4与HgCl2反应得到含Mo-Hg键的化合物。用(Ph3P)2Mo(CO)4和(Ph3P)2Ni(CO)2二元催化体系,在适当温度和压力下对甲醇羰基化反应进行初步研究,得到了初步研究,得到了醋酸和醋酸甲酯。该催化过程对甲醇的转化率可达92%,对醋酸和醋酸甲酯的选择性可达68%。     

钛,锆和铪羰基化合物M(CO)_n(M=Ti,Zr,Hf;n=4～7)的理论研究

利用密度泛函方法对标题化合物的平衡几何、热化学及振动频率进行了理论预测,发现这3种金属原子都有相似的M(CO)n(n=4～7)结构.全局最低构型对M(CO)7都是单态C3v戴帽八面体7S-1,对M(CO)6都是三重态D3d畸变八面体6T(而对应的单重态M(CO)5仅比它低不到21 kJ·mol-1).对M(CO)n(n=5,4)都是三重态6S-1,其构型分别为从6T中移去1个或2个CO基的衍生物5T和4T.此外,五重态的D3h的三角双锥M(CO)5和单态的Td四面体M(CO)4以及能量更高的含有C和O同时与金属成键的独特配位CO基的M(CO)6和M(CO)3也被发现.最后,给出M(CO)7→M(CO)6+CO反应的离解能.并讨论了金属18价电子的Ti(CO)7存在的可能性.     

SYNTHESIS,CHARACTERIZATION AND CRYSTAL STRUCTURES OF η~5-CH_3C_5H_4)M(CO)_2NO AND(η~5-CH_3C_5H_4)M(μ_3-NH)(μ_2-NO)(μ_2-CO)Fe_2(CO)_6(M=Mo or W)

Synthesis of complexes(η~5-CH_3C_5H_4)M(CO)_2NO(M=Mo,I;M=W,II)and clusters(η~5-CH_3C_5H_4)M(μ~3-NH)(μ~2-NO) (μ~2-CO)Fe_2(CO)_6(M=Mo,III:M=W,IV),based on the reaction of (η~5-C5_H_4)M(CO)_3Cl with Na[Fe(CO)_3NO] at room tem-perature,have been demonstrated,The crystal structures of II and IV arealso presented.     

A novel synthesis of metallogermacyclopropane and molybdenum bis(iminophosphorano)carbene complexes from bisgermavinylidene

The reaction of bisgermavinylidene [(Me3SiN=PPh2)2C=Ge-->Ge=C(PPh2=NSiMe3)2] (1) with M(CO)5(THF) ( M = Cr, W, Mo) afforded the metallagermacyclopropane [(Me-3SiN=PPh2)2CGeM(CO)3[M(CO)5]] [M = W (2), Cr (3), Mo (4)]; in one of the reactions, compound 4 reacts further to give a "pincer" carbene complex [(CO)3Mo[C(Ph2P=NSi Me3)2]] (5); the X-ray structures of compounds 2 and 5 have been determined.     

Cyanide-bridged linkage isomers with catecholateruthenium(II) centres bound to Mn(I) or M(alkyne) units

Two series of stable cyanide-bridged linkage isomers, namely [(o-O2C6Cl4)(Ph3P)(OC)2Ru(mu-XY)MnL(NO)(eta-C5Me5)] (XY = CN or NC, L = CNBu(t) or CNXyl) and [(o-O2C6Cl4)L(OC)2Ru(mu-XY)M(CO)(PhC-CPh)Tp'] {M = Mo or W, L = PPh3 or P(OPh)3, Tp' = hydrotris(3,5-dimethylpyrazolyl)borate} have been synthesised; pairs of isomers are distinguishable by IR spectroscopy and cyclic voltammetry. The molecular structure of [(o-O2C6Cl4)(Ph3P)(OC)2Ru(mu-NC)Mo(CO)(PhC-CPh)Tp'] has the catecholate-bound ruthenium atom cyanide-bridged to a Mo(CO)(PhC[triple band]CPh)Tp' unit in which the alkyne acts as a four-electron donor; the alignment of the alkyne relative to the Mo-CO vector suggests the fragment (CN)Ru(CO)2(PPh3)(o-O2C6Cl4) acts as a pi-acceptor ligand. The complexes [(o-O2C6Cl4)(Ph3P)(OC)2Ru(mu-XY)Mn(NO)L(eta-C5Me5)] undergo three sequential one-electron oxidation processes with the first and third assigned to oxidation of the ruthenium-bound o-O2C6Cl4 ligand; the second corresponds to oxidation of Mn(I) to Mn(n). The complexes [(o-O2C6Cl4)L(OC)2Ru(mu-XY)M(CO)(PhC[triple band]CPh)Tp'] are also first oxidised at the catecholate ligand; the second oxidation, and one-electron reduction, are based on the M(CO)(PhC[triple band]CPh)Tp' fragment. Chemical oxidation of [(o-O,C6Cl4)(Ph3P)(OC)2Ru(mu-XY)MnL(NO)(eta-C5Me5)] with [Fe(eta-C5H4COMe)(eta-C5H5)][BF4], or of [(o-O2C6Cl4)L(OC)2Ru(mu-XY)M(CO)(PhC[triple band]CPh)Tp'] with AgBF4, gave the paramagnetic monocations [(o-O2C6Cl4)(Ph3P)(OC)2Ru(mu-XY)MnL(NO)(eta-C5Me5)]+ and [(o-O2C6Cl4)L(OC)2Ru(mu-XY)M(CO)(PhC[triple band]CPh)Tp']+, the ESR spectra of which are consistent with ruthenium-bound semiquinone ligands. Linkage isomers are distinguishable by the magnitude of the 31P hyperfine coupling constant; complexes with N-bound Ru(o-O2C6Cl4) units also show small hyperfine coupling to the nitrogen atom of the cyanide bridge.     

A series of dinuclear homo- and heterometallic complexes with two or three bridging sulfido ligands derived from the tungsten tris(sulfido) complex [Et(4)N][(Me(2)Tp)WS(3)] (Me(2)Tp = hydridotris(3,5-dimethylpyrazol-1-yl)borate)

The generation of heterobimetallic complexes with two or three bridging sulfido ligands from mononuclear tris(sulfido) complex of tungsten [Et(4)N][(Me(2)Tp)WS(3)] (1; Me(2)Tp = hydridotris(3,5-dimethylpyrazol-1-yl)borate) and organometallic precursors is reported. Treatment of 1 with stoichiometric amounts of metal complexes such as [M(PPh(3))(4)] (M = Pt, Pd), [(PtMe(3))(4)(micro(3)-I)(4)], [M(cod)(PPh(3))(2)][PF(6)] (M = Ir, Rh; cod = 1,5-cyclooctadiene), [Rh(cod)(dppe)][PF(6)] (dppe = Ph(2)PCH(2)CH(2)PPh(2)), [CpIr(MeCN)(3)][PF(6)](2) (Cp = eta(5)-C(5)Me(5)), [CpRu(MeCN)(3)][PF(6)], and [M(CO)(3)(MeCN)(3)] (M = Mo, W) in MeCN or MeCN-THF at room temperature afforded either the doubly bridged complexes [Et(4)N][(Me(2)Tp)W(=S)(micro-S)(2)M(PPh(3))] (M = Pt (3), Pd (4)), [(Me(2)Tp)W(=S)(micro-S)(2)M(cod)] (M = Ir, Rh (7)), [(Me(2)Tp)W(=S)(micro-S)(2)Rh(dppe)], [(Me(2)Tp)W(=S)(micro-S)(2)RuCp] (10), and [Et(4)N][(Me(2)Tp)W(=S)(micro-S)(2)W(CO)(3)] (12) or the triply bridged complexes including [(Me(2)Tp)W(micro-S)(3)PtMe(3)] (5), [(Me(2)Tp)W(micro-S)(3)IrCp][PF(6)] (9), and [Et(4)N][(Me(2)Tp)W(micro-S)(3)Mo(CO)(3)] (11), depending on the nature of the incorporated metal fragment. The X-ray analyses have been undertaken to clarify the detailed structures of 3-5, 7, and 9-12.     

（CH3）3NO存在下M（CO）5（M＋Fe,Ru,Os）的CO取代反应动力学研究

在(CH_3)_3NO存在下,PPh_3取代M(CO)_5(M=Fe,Ru,Os)中CO的反应速度遵循二级速度定律,分别与[M(CO)_5]和[(CH_3)_3NO]的一次方成正比,与[PPh_3]无关。反应速度按FeRu>Os的次序约减小4倍。 1 实验方法 典型的动力学实验中,将(CH_3)_3NO的C_2H_5OH溶液和PPh_3的己烷溶液分别用注射器加到体积合适的烧瓶中,再注入Fe(CO)_5并迅速震荡烧瓶,再取出一部分反应液立即注入充N_2     

Experimental and theoretical studies of carbodiphosphorane-CX2 adducts with unusual bonding situations: preparation, crystal structures, and bonding analyses of S2CC(PPh3)2, O2CC(PPh3)2, and [(CO)4MS2CC(PPh3)2] (M = Cr, Mo, W)

We report about the first X-ray structure analyses of the CS2 and CO2 adducts with carbodiphosphorane C(PPh3)2 and the synthesis and X-ray structure analysis of group 6 carbonyl complexes with compound S2CC(PPh3)2 as a ligand [(CO)4MS2CC(PPh3)2] (M = Cr, Mo, W). The nature of the carbon-carbon bonding in X2CC(PPh3)2 and in the model compounds X2CC(PH3)2 and the metal-ligand bonding in [(CO)4MoS2CC(PH3)2] have been analyzed with charge and energy decomposition methods using DFT calculations. Carbodiphosphoranes C(PR3)2 are double electron pair donors having sigma- and pi-carbon lone-pair orbitals as the two highest occupied MOs.     

B(C6F5)3 adducts of transition metal acyl compounds

The transition metal acyl compounds [Co(L)(CO)3(COMe)] (L = PMe3, PPhMe2, P(4-Me-C6H4)3, PPh3 and P(4-F-C6H4)3), [Mn(CO)5(COMe)] and [Mo(PPh3)(eta(5)-C5H5)(CO)2(COMe)] react with B(C6F5)3 to form the adducts [Co(L)(CO)3(C{OB(C6F5)3}Me)] (L = PMe3, 1, PPhMe2, 2, P(4-Me-C6H4)3, 3, PPh3, 4, P(4-F-C6H4)3), 5, [Mn(CO)5(C{OB(C6F5)3}Me)] 6 and [Mo(eta(5)-C5H5)(PPh3)(CO)2(C{OB(C6F5)3}Me)], 7. Addition of B(C6F5)3 to a cooled solution of [Mo(eta(5)-C5H5)(CO)3(Me)], under an atmosphere of CO gave [Mo(eta(5)-C5H5)(CO)3(C{OB(C6F5)3}Me)] 8. In the presence of adventitious water, the compound [Co{HOB(C6F5)3}2{OP(4-F-C6H4)3}2] 9, was formed from [Co(P(4-F-C6H4)3)(CO)3(C{OB(C6F5)3}Me)]. The compounds 4 and 9 have been structurally characterised. The use of B(C6F5)3 as a catalyst for the CO-induced migratory-insertion reaction in the transition metal alkyl compounds [Co(PPh3)(CO)3(Me)], [Mn(CO)5(Me)], [Mo(eta(5)-C5H5)(CO)3(Me)] and [Fe(eta(5)-C5H5)(CO)2(Me)] has been investigated.     

New Group 6 metal carbonyl derivatives of 2-(2'(-pyridyl)benzimidazole: synthesis and spectroscopic studies

Reaction of Cr(CO)(6) with 2-(2'-pyridyl)benzimidazole (pbiH) under reduced pressure resulted in the formation of the dinuclear complex [Cr(2)(CO)(6)(pbiH)(2)]. Infra-red (IR) spectroscopy revealed the presence of terminal and bridge Cr-CO bonds. Interaction of M(CO)(6), M=Cr, Mo and W, with pbiH in the presence of 2,2'-bipyridine (bpy) gave the tetracarbonyl complexes [M(CO)(4)(pbiH)].bpy. Spectroscopic studies of the complexes indicated the presence of hydrogen bonding between the bpy nitrogen and the NH group of pbiH. Reactions of M(CO)(6) with pbiH in the presence of PPh(3) gave the tricarbonyl monosubstituted derivatives [M(CO)(3)(PPh(3))(pbiH)]. The spectroscopic studies of the complexes suggested the proposed structures.     

Alternativ-Liganden. VIII. Chelatkomplexe des Typs M(CO)4(Me2XGeMe2CH2X′Me2) (M = Cr,Mo, W; X,X′ = N,P, As; Me = CH3)

Chelate Complexes of the Type M(CO)₄(Me₂XGeMe₂CH₂X′Me₂) (M) = Cr, Mo, W; X, X′ = N, P, As; Me = CH₃) The ligands (Me₂)XGeMe₂CH₂X′Me₂ (M) = Cr, Mo, W) react with M(CO)₄norbor (norbor = Norbornadiene) (M = Cr, Mo, W) yielding the chelate complexes M(CO)₄(Me)₂XGeMe₂CH₂X′Me₂). compounds of low thermal stability are formed with the ligands (Me₂NGeMe₂CH₂X′Me₂ because of the weak donor ability of the GeNMe₂ group and with Me₂AsGeMe₂CH₂NMe₂ caused by strong steric ring tension. The new compounds are characterized by analytical and spectroscopic (n.m.r., i.r., m.s.) investigations.